Novel image dye-providing materials, photographic products and processes

ABSTRACT

There are disclosed diffusion transfer color processes and products which employ novel image dye-providing materials which provide image dyes having the chromophoric system represented by the formula ##STR1## wherein A is ##STR2## X is H, alkyl, aryl or substituted aryl; W is H or alkyl, R is H or alkyl; m and n are each integers of from 2 to 6. 
     The image dye-providing material includes a diffusion control moiety such as a hydroquinonyl group and may be diffusible or nondiffusible as a function of the diffusion control moiety.

BACKGROUND OF THE INVENTION

This invention relates to photography in general and, more particularly,to dyes which are useful in providing diffusion transfer color imagesand to photographic products and processes employing such dyes.

Multicolor images formed in accordance with the principles ofsubtractive color photography employ yellow, magenta and cyan imagedyes. The yellow dye ideally transmits only green and red light andabsorbs only blue light, and thus is sometimes referred to as "minusblue". In like manner, the magenta ("minus green") dye ideally absorbsonly green light and transmits only blue and red light, and the cyan("minus red") dye ideally absorbs only red light and transmits only blueand green light. Unfortunately, the dyes available for use insubtractive color photography are not "ideal" dyes, but tend to absorbsome of the light that they ideally should transmit. This extraabsorption results in less effective reproduction by the final image ofone or more colors present in the original subject.

This problem may be illustrated by considering the reproduction of bluelight: a multicolor photosensitive element, containing a blue-sensitivesilver halide layer, a green-sensitive silver halide layer and ared-sensitive silver halide layer, said silver halide layers havingassociated therewith, respectively, a yellow image dye-providingmaterial, a magenta image dye-providing material, and a cyan imagedye-providing material, is exposed to blue light in an amount effectiveto fully expose the blue-sensitive layer. Only the blue-sensitive silverhalide layer is exposed; the green-sensitive and red-sensitive silverhalide emulsion layers remain unexposed. If such an exposedphotosensitive element were processed by diffusion transfer techniques,the yellow image dye-providing material would remain in the developedphotosensitive element (negative component) but magenta and cyan imagedyes would be transferred to the image-receiving layer (positivecomponent). Since the magenta and cyan image dyes are "minus green" and"minus red" respectively, the combination of magenta and cyan dyesappear blue, i.e., they transmit blue light to the viewer and absorbgreen and red, thus reproducing the blue record of the original subject.

In the art of photography there is a continuing search for newimage-forming dyes. The present application is drawn to novel imagedye-providing materials which are useful in photography.

SUMMARY OF THE INVENTION

It is therefore the object of this invention to provide novel compounds.

It is another object to provide image-forming dyes which are useful inphotography.

It is a further object to provide dye developers which are useful inphotographic diffusion transfer applications.

Still another object is to provide image dye-providing materials whichare useful in dye release diffusion transfer processes, for example, ofthe redox dye release or the silver-catalyzed dye release types.

Yet another object is to provide novel photographic products andprocesses.

A further object is to provide novel diffusion transfer photographicproducts and processes.

BRIEF SUMMARY OF THE INVENTION

These and other objects and advantages are accomplished in accordancewith the invention by providing materials which provide image dyeshaving the chromophoric system represented by the formula ##STR3##wherein A is ##STR4## X is H, alkyl, preferably having from 1 to 6carbon atoms, aryl such as phenyl or naphthyl, or aryl substituted withsubstituents such as SO₃.sup.⊖, CO₂.sup.⊖, or alkyl, preferably havingfrom 1 to 6 carbon atoms; W is H or alkyl, preferably having from 1 to 6carbon atoms; R is H or alkyl, preferably having from 1 to 6 carbonatoms; m and n are each integers of from 2 to 6.

It will be understood that compounds within Formula A may be representedby the resonance form such as, for example, ##STR5## Both resonanceforms of the chromophoric system are intended to be encompassed byFormula A.

In a preferred embodiment X is ##STR6## wherein R₁ is H, SO₃.sup.⊖,CO₂.sup.⊖ or alkyl, preferably alkyl having from 1 to 6 carbon atoms. R₁is preferably SO₃.sup.⊖ since such compounds typically exhibit goodstability in alkali.

The image dye-providing materials include a diffusion control moietysuch as a hydroquinonyl group and may be diffusible or nondiffusible asa function of the diffusion control moiety.

In the photographic diffusion transfer processes of the invention thedesired image is obtained by processing an exposed photosensitive silverhalide material with a processing composition distributed between twosheet-like elements, one of said elements including said photosensitivematerial. The processing composition is so applied and confined withinand between the two sheet-like elements as not to contact or wet outersurfaces of the superposed elements, thus providing a film unit or filmpacket whose outer surfaces are dry. The processing composition may beviscous or nonviscous and preferably is distributed from a single-usecontainer; such pressure rupturable processing composition containersare frequently referred to as "pods". The final image may be monochromeor multicolor and is formed in an image-receiving layer included in oneof said sheet-like elements.

As is well known in diffusion transfer photography, the imagedye-providing materials which may be utilized in such processesgenerally may be characterized as either (1) initially soluble ordiffusible in the processing composition but which are selectivelyrendered nondiffusible imagewise as a function of development; or (2)initially insoluble or nondiffusible in the processing composition butwhich selectively provide a diffusible product imagewise as a functionof development. The image dye-providing materials may be complete dyesor dye intermediates, e.g., color couplers. The requisite differentialin mobility or solubility may, for example, be obtained by a chemicalreaction such as a redox reaction, a coupling reaction or a clevagereaction.

The image dye providing materials which are capable of providing imagedyes containing the chromophoric system of Formula A may be provided byincluding a diffusion control substituent, Y, which substituent includesa diffusion control moiety, D. One such group of image dye-providingmaterials is represented by the formula ##STR7## wherein B is ##STR8##each Y is a substituent containing a diffusion control moiety, and eachq is 0 or 1 provided that at least one q is 1.

In such image dye-providing materials the diffusion control substituentmay be represented by

    --E-- Dev

wherein Dev is a hydroquinonyl group and E is a covalent bond or adivalent linking group, for example, alkylene.

Image dye-providing materials within Formula C, as a function of theparticular diffusion control moiety D which is present, are suitable foruse in diffusion transfer processes employing either initiallydiffusible or initially nondiffusible image dye-providing materials.Typical diffusion control moieties include hydroquinonyl groups, colorcoupling groups, sulfonamido phenol groups which cleave or ring closefollowing oxidation to release a diffusible dye or dye intermediate, andthiazolidine groups whose cleavage is silver catalyzed. The diffusioncontrol moiety D may be attached by a covalent bond or a divalentorganic radical, for example, an alkylene radical, to complete thediffusion control substituent Y. Further, where the image dye-providingmaterial is initially diffusible a suitable ballast group, for example,a long chain alkyl group, may be attached to the diffusion controlmoiety.

BRIEF DESCRIPTION OF THE DRAWING

For a better understanding of the invention as well as other objects andadvantages of the invention and further features thereof, reference ismade to the following detailed description of various preferredembodiments thereof taken in conjunction with the drawing wherein theFIGURE is the absorption spectrum of one of the preferred imagedye-providing materials of the invention.

DESCRIPTION OF THE PREFERRED EMBODIMENT

Preferred image dye-providing materials of the invention are representedby the formulas: ##STR9## The FIGURE illustrates the absorption spectrumof dye I as obtained from a 2×10⁻⁵ molar solution in methyl cellosolve.The dye has a λ max=632 nm and ε=87,500. ##STR10##

The image dye-providing materials of the invention are of variouscolors. For example, within Formula A, when A is ##STR11## and m and nare each 2, the compounds are typically cyan in solution and in aphotograph and when m and n are each 3 the compounds are typically bluein solution and in photographs; when m and n are each 4 or 5 thecompounds typically are magenta in solution and in photographs.

In a particularly preferred embodiment of the invention the diffusioncontrol moiety is a hydroquinonyl moiety and the resulting dyedevelopers are initially diffusible image dye-providing materials. Asdescribed in U.S. Pat. No. 2,983,606 a photosensitive element containinga dye developer and a silver halide emulsion is photoexposed and aprocessing composition applied thereto, for example, by immersion,coating, spraying, flowing, etc., in the dark. The exposedphotosensitive element is superposed prior to, during, or after theprocessing composition is applied, on a sheet-like support element whichmay be utilized as an image-receiving element. In a preferredembodiment, the processing composition is applied to the exposedphotosensitive element in a substantially uniform layer as thephotosensitive element is brought into superposed relationship with theimage-receiving layer. The processing composition, positionedintermediate the photosensitive element and the image-receiving layer,permeates the emulsion to initiate development of the latent imagecontained therein. The dye developer is immobilized or precipitated inexposed areas as a consequence of the development of the latent image.This immobilization is apparently, at least in part, due to a change inthe solubility characteristics of the dye developer upon oxidation andespecially as regards its solubility in alkaline solutions. It may alsobe due in part to a tanning effect on the emulsion by oxidizeddeveloping agent, and in part to a localized exhaustion of alkali as aresult of development. In unexposed and partially exposed areas of theemulsion, the dye developer is unreacted and diffusible and thusprovides an imagewise distribution of unoxidized dye developer,diffusible in the processing composition, as a function of thepoint-to-point degree of exposure of the silver halide emulsion. Atleast part of this imagewise distribution of unoxidized dye developer istransferred, by imbibition, to a superposed image-receiving layer orelement, said transfer substantially excluding oxidized dye developer.The image-receiving layer receives a depthwise diffusion, from thedeveloped emulsion, of unoxidized dye developer without appreciablydisturbing the imagewise distribution thereof to provide a reversed orpositive color image of the developed image. The image-receiving elementmay contain agents adapted to mordant or otherwise fix the diffused,unoxidized dye developer. In a preferred embodiment of said U.S. Pat.No. 2,983,606 and in certain commercial applications thereof, thedesired positive image is revealed by separating the image-receivinglayer from the photosensitive element at the end of a suitableimbibition period. Alternatively, as also disclosed in said U.S. Pat.No. 2,983,606, the image-receiving layer need not be separated from itssuperposed contact with the photosensitive element, subsequent totransfer image formation, if the support for the image-receiving layer,as well as any other layers intermediate said support andimage-receiving layer, is transparent and a processing compositioncontaining a substance, e.g., a white pigment, effective to mask thedeveloped silver halide emulsion or emulsions is applied between theimage-receiving layer and said silver halide emulsion or emulsions.

Dye developers, as noted in said U.S. Pat. No. 2,983,606, are compoundswhich contain, in the same molecule, both the chromophoric system of adye and also a silver halide developing function. By "a silver halidedeveloping function" is meant a grouping adapted to develop exposedsilver halide. A preferred silver halide development function is ahydroquinonyl group. In general, the development function includes abenzenoid developing function, that is, an aromatic developing groupwhich forms quinonoid or quinone substances when oxidized.

Multicolor images may be obtained using dye developers in diffusiontransfer processes by several techniques. One such techniquecontemplates obtaining multicolor transfer images utilizing dyedevelopers by employment of an integral multilayer photosensitiveelement, such as is disclosed in the aforementioned U.S. Pat. No.2,983,606 and in U.S. Pat. No. 3,345,163, wherein at least twoselectively sensitized photosensitive strata, superposed on a singlesupport, are processed, simultaneously and without separation, with asingle common image-receiving layer. A suitable arrangement of this typecomprises a support carrying a red-sensitive silver halide emulsionstratum, a green-sensitive silver halide emulsion stratum and ablue-sensitive silver halide emulsion stratum, said emulsions havingassociated therewith, respectively, for example, a cyan dye developer, amagenta dye developer and a yellow dye developer. The dye developer maybe utilized in the silver halide emulsion stratum, for example in theform of particles, or it may be disposed in a stratum behind theappropriate silver halide emulsion strata. Each set of silver halideemulsion and associated dye developer strata may be separated from othersets by suitable interlayers, for example, by a layer or stratum ofgelatin or polyvinyl alcohol. In certain instances, it may be desirableto incorporate a yellow filter in front of the green-sensitive emulsionand such yellow filter may be incorporated in an interlayer. However,where desirable, a yellow dye developer of the appropriate spectralchartacteristics and present in a state capable of functioning as ayellow filter may be so employed and a separate yellow filter omitted.

Particularly useful products for obtaining multi-color dye developerimages are disclosed in U.S. Pat. No. 3,415,644. This patent disclosesphotographic products wherein a photosensitive element and animage-receiving element are maintained in fixed relationship prior toexposure, and this relationship is maintained as a laminate afterprocessing and image formation. In these products, the final image isviewed through a transparent (support) element against alight-reflecting, i.e., white background. Photoexposure is made throughsaid transparent element and application of the processing compositionprovides a layer of light-reflecting material to provide a whitebackground. The light-reflecting material (referred to in said patent asan "opacifying agent") is preferably titanium dioxide, and it alsoperforms an opacifying function, i.e., it is effective to mask thedeveloped silver halide emulsions so that the transfer image may beviewed without interference therefrom, and it also acts to protect thephotoexposed silver halide emulsions from post-exposure fogging by lightpassing through said transparent layer if the photoexposed film unit isremoved from the camera before image-formation is completed.

U.S. Pat. No. 3,647,437 is concerned with improvements in products andprocesses disclosed in said U.S. Pat. No. 3,415,644, and discloses theprovision of light-absorbing materials to permit such processes to beperformed, outside of the camera in which photoexposure is effected,under much more intense ambient light conditions. A light-absorbingmaterial or reagent, preferably a pH-sensitive phthalein dye, isprovided so positioned and/or constituted as not to interfere withphotoexposure but so positioned between the photo-exposed silver halideemulsions and the transparent support during processing afterphotoexposure as to absorb light which otherwise might fog thephotoexposed emulsions. Furthermore, the light-absorbing material is sopositioned and/or constituted after processing as not to interfere withviewing the desired image shortly after said image has been formed. Inthe preferred embodiments, the light-absorbing material, also sometimesreferred to as an optical filter agent, is initially contained in theprocessing composition together with a light-reflecting material, e.g.,titanium dioxide. The concentration of the light-absorbing dye isselected to provide the light transmission opacity required to performthe particular process under the selected light conditions.

In a particularly useful embodiment, the light-absorbing dye is highlycolored at the pH of the processing composition, e.g., 13-14, but issubstantially non-absorbing of visible light at a lower pH, e.g., lessthan 10-12. This pH reduction may be effected by an acid-reactingreagent appropriately positioned in the film unit, e.g., in a layerbetween the transparent support and the image-receiving layer.

The dye developers are preferably selected for their ability to providecolors that are useful in carrying out subtractive color photography,that is, the previously mentioned cyan, magenta and yellow. The dyedevelopers employed may be incorporated in the respective silver halideemulsion or, in the preferred embodiment, in a separate layer behind therespective silver halide emulsion, and such a layer of dye developer maybe applied by use of a coating solution containing the respective dyedeveloper distributed, in a concentration calculated to give the desiredcoverage of dye developer per unit area, in a film-forming natural, orsynthetic, polymer, for example, gelatin, polyvinyl alcohol, and thelike, adapted to be permeated by the processing composition.

Other diffusion transfer products and processes in which the dyedevelopers of the present invention may be utilized are described inU.S. Pat. Nos. 3,573,043 and 3,594,165.

As described previously, the image dye-providing materials of theinvention are not restricted to dye developers but rather may includemany other types of initially diffusible and initially nondiffusibleimage dye-providing materials. Thus, for example, an initiallydiffusible coupling dye which is useful in the diffusion transferprocess described in U.S. Pat. No. 3,087,817 may be provided bysubstituting one or both of the indolinyl groups or the anilino groupwith a color coupling moiety such as a phenol or naphthol having a freeposition para to the hydroxyl group. An example of such a coupling dyeaccording to the invention is represented by the formula ##STR12## Thisdye is initially diffusible but is rendered nondiffusible by couplingwith the oxidation product of a color developer, e.g., ap-phenylenediamine or a p-aminophenol, to form a less diffusibleproduct. If the coupling position is substituted by a substituent whichrenders the dye initially nondiffusible by virtue of a ballast group andwhich substituent is displaceable upon coupling, such a dye may beemployed to provide a diffusible dye where coupling occurs employing theprinciples described in U.S. Pat. No. 3,227,550.

An initially nondiffusible "redox dye releaser" dye useful in thediffusion transfer process described in U.S. Pat. No. 4,076,529 may beprovided by substituting one or both of the indolinyl groups or theanilino group with a sulfonamidophenol or sulfonamidonaphthol group. Anexample of such a dye according to the invention is represented by theformula ##STR13## Other sulfonamidophenol and sulfonamidonaphthol groupsknown in the art, e.g. such as those described in U.S. Pat. Nos.4,053,312 and 4,055,428, which cleave, in alkaline solution, at thesulfonamido group following oxidation may be used in place of thep-sulfonamidonaphthol group shown above.

Another class of initially nondiffusible image dye-providing materials(described in U.S. Pat. No. 3,433,939) release a diffusible dyefollowing oxidation and intramolecular ring closure. An imagedye-providing material of this type according to the invention isrepresented by the formula ##STR14##

Other image dye-providing materials which cleave in alkali followingoxidation may be provided by a compound within Formula C wherein Y is--O-- or --S-- and the hydroquinonyl group contains a ballast groupe.g., C₁₅ H₃₁ in accordance with the disclosure of U.S. Pat. No.3,725,062. An example of such a compound is represented by the formula##STR15##

It should be understood that although the ballast group in the aboveillustrated compounds is a long chain alkyl group, other ballast groupsknown in the art may also be used.

In the use of a nondiffusible image dye-providing material whichreleases a diffusible image dye-providing material following oxidationin an alkaline environment, the requisite oxidation may be effected bythe oxidation product of a mobile developing agent used to develop thephotoexposed silver halide emulsion. A particularly effective developingagent for this purpose is 1-phenyl-4,4-dimethyl-3-pyrazolidone; othersuitable developing agents are known in the art.

Development is advantageously effected in the presence of an oniumcompound, particularly a quaternary ammonium compound, in accordancewith the disclosure of U.S. Pat. No. 3,173,786. Quaternary ammoniumcompounds which form an active methylene compound in alkali areespecially useful.

Development may be effected in the presence of a colorless auxiliaryaccelerating developing agent such as, for example, a 3-pyrazolidone ora hydroquinone such as 4'-methylphenylhydroquine, which may be initiallyarranged in a layer of the photosensitive element or in the processingcomposition.

In another preferred embodiment of the invention the diffusion controlmoiety is a thiazolidine group whose cleavage is silver catalyzed. Asdescribed in U.S. Pat. No. 3,719,489, image dye-providing materials ofthis type are photographically inert in the photographic processingcomposition but are capable of undergoing cleavage in the presence of animagewise distribution of silver ions and/or soluble silver complexcontaining silver ions made available as a function of development toliberate a reagent in an imagewise distribution corresponding to that ofsaid silver ion and/or said complex. Dye III is an example of such animage dye-providing material according to the invention.

The invention will now be described further in detail with respect tospecific preferred embodiments by way of examples, it being understoodthat these are illustrative only and the invention is not intended to belimited to the materials, conditions, process parameters, etc., recitedtherein. All parts and percentages are by weight unless otherwiseindicated.

EXAMPLE I

15 gms (0.102 m) of indoline formamide were melted in a 250 ml roundbottom flask over a free flame. The melt was cooled in an icebath andswirled as it cooled to distribute the material over the flask as thematerial solidified. To the flask there were added 34.7 ml ofchlorosulfonic acid. The flask was removed from the ice bath and thecontents swirled until all the indoline formamide was dissolved (5-10minutes). The solution was then heated on a steam bath for 10 minutes.The flask was then cooled and the contents slowly poured into 200 ml ofice water cooled in an ice bath. A sticky precipitate was formed whichslowly solidified. The precipitate was collected by filtration,dissolved in chloroform and dried over anhydrous calcium sulfate.Evaporation of the filtered chloroform solution gave 16.6 gms. (66%yield) of crude ##STR16## which was then recrystallized fromchloroform/petroleum ether.

In 50 ml of pyridine cooled in an ice bath there were dissolved 10 gms(0.035 m) of ##STR17## and to the solution there were added 8.6 gms(0.035 m) of the previous product while maintaining the temperaturebelow 20° C. The reaction mixture was stirred overnight. The mixture waspoured into dilute HCl and then filtered to collect a gummy residuewhich is represented by the formula ##STR18##

The residue was dissolved in methanol and HCl gas was bubbled throughthe solution for about 15 minutes. The solution was allowed to standovernight and the solvent evaporated off under vacuum. An oily residuewas obtained which solidified upon standing over two days. The solid wasdissolved in chloroform, the solution shaken with aqueous potassiumcarbonate and the chloroform layer dried over anhydrous calcium sulfate.After evaporation of the chloroform the solid product, represented bythe formula ##STR19## was recrystallized from isopropyl alcohol.

A mixture of 9.0 gms (0.0193 m) of this product, 3.9 gms (0.0096 m) ofdichlorosulfonefluorescein, 0.4 gm of magnesium oxide and 10 ml ofdimethylsulfoxide was heated with stirring in an oil bath at 135° C. Thereaction was monitored by thin layer chromatography (10/90methanol/chloroform, by volume). After 20 minutes the starting materialshad disappeared and TLC showed only one cyan spot. After cooling thereaction mixture slightly, 100 ml of water were added and the solidifieddye was filtered off as a blue solid. The solid was washed well withwater and dried to give a quantitative yield of a blocked dye developer.

6.0 gms (0.0047 m) of the blocked dye developer were dissolved in 400 mlof chloroform and the solution cooled to -78° C. in a dry ice-acetonebath. To this solution there was added, with stirring, a solution of12.5 gms (0.05 m) of boron tribromide in 25 ml of chloroform. Themixture was stirred at room temperature overnight and 200 ml of watercontaining 20 ml of hydrochloric acid were added cautiously. The mixturewas stirred and refluxed for one hour. The mixture was then filteredwhile hot. The resulting blue solid was washed well with water and driedto give 4.8 gms. (85% yield) of dye I, λmax=635 nm, ε=85,000.

To illustrate the utility of the dye developer in photographicapplications a film unit was prepared. The negative element of the filmunit comprised: a subcoated transparent polyester photographic filmbase; a cyan dye developer layer comprising about 215 mg./m² of the dyedeveloper represented by dye I and about 215 mg./m² of cellulose acetatehydrogen phthalate; a red sensitive gelatino silver iodobromide (1.075microns) emulsion layer coated at a coverage of about 538 mg./m² ofsilver and about 956 mg./m² of gelatin; and an overcoat of about 323mg./m² of gelatin and about 81 mg./m² of 4'-methylphenylhydroquinone.

The image-receiving element comprised a 4 mil thick transparentsubcoated polyethylene terephthalate film base with the following layerscoated thereon in succession:

1. as a polymeric acid layer approximately 9 parts of a 1/2 butyl esterof polyethylene/maleic anhydride copolymer and 1 part of polyvinylbutyral coated at a coverage of about 26,372 mgs./m² ;

2. a timing layer containing about 4575 mgs./m² of a 60-30-4-6tetrapolymer of butylacrylate, diacetone acrylamide, styrene andmethacrylic acid including about 8% polyvinylalcohol; and

3. a polymeric image receiving layer of: (a) 3 parts of a mixture of 2parts polyvinylalcohol and 1 part poly-4-vinylpyridine and (b) 1 part ofa graft copolymer comprised of 4-vinylpyridine (4VP) and vinylbenzyltrimethylammonium chloride (TMQ) grafted onto hydroxyethyl cellulose(HEC) at a ratio of HEC/4VP/TMQ of 2.2/2.2/1 coated at a coverage ofabout 3230 mgs./m².

The film unit was processed with a processing composition comprising:

    ______________________________________                                                            GMS/100ccH.sub. 2 O                                       ______________________________________                                        Water                 100 cc                                                  Polyethylene glycol   1.23                                                    Colloidal silica      1.25                                                    N-Hydroxyethyl-N,N',N'-tris-                                                  carboxymethyl ethylene diamine                                                                      1.89                                                    Lithium nitrate       0.22                                                    Carboxymethyl cellulose                                                                             2.31                                                    Titanium dioxide      95.28                                                   Potassium hydroxide   8.04                                                    Lithium hydroxide     0.26                                                    N-benzyl-α-picolinium bromide                                                                 2.85                                                    N-phenethyl-α-picolinium bromide                                                              1.64                                                    Benzotriazole         1.26                                                    5-bromo-6-methyl-4-azabenzimidazole                                                                 0.06                                                    Bis-(β-aminoethyl)sulfide                                                                      0.05                                                    6-methyl uracil       0.67                                                    6-benzylamino purine  0.89                                                    ______________________________________                                    

The negative was exposed on a sensitometer to a neutral test exposurescale, or step wedge, with red and blue light successively (2meter-candle-seconds each) and processed by passing the negative andimage-receiving elements in superposed relationship, through a pair ofrollers at a gap spacing of 0.0020 inch while distributing theprocessing composition between said elements. The resulting laminate waskept in the dark for 10 minutes to avoid fogging the developing silverhalide emulsion by light passing through the transparent film base. Whenbrought into the light a well defined positive cyan image (reflectiondensity to red light D_(max) =0.90, D_(min) =0.28) was visible throughthe transparent base of the image-receiving element against the whitelayer of titanium dioxide provided by the processing composition,without separating the superposed elements.

EXAMPLE II

To a mixture of 60 ml methanol and 30 ml pyridine there were added 12.3gms (0.0421 m) of ##STR20## and 12.3 gms (0.176 m) of hydroxylaminehydrochloride and the reaction mixture refluxed for 1 hour on a steambath. The reaction mixture was poured into 420 ml of water and stirred.A gummy product was obtained from which the water was decanted andanother volume of water added. The material continued to be gummy so thewater was decanted and the material dissolved in chloroform, extractedonce with water and dried. Thin layer chromatography (1/1ether/petroleum ether, by volume) showed no starting materials present.

Solvent was stripped from the residue under vacuum leaving a semi-solid.Diethyl ether was added to the semisolid and it was scratched with aglass rod resulting in the formation of a pale yellow solid representedby the formula ##STR21## The solid was air-dried to give 2.5 gms.

This product (2.5 gms) and 87.5 gms of polyphosphoric acid were heatedat 135° C. for 20 minutes and then poured into 80 ml of water. A yellowsolid formed. The solid was collected and recrystallized fromtetrahydrofuran. The product is represented by the formula ##STR22##

This previous product (1.0 gm, 0.0032 m) and 0.97 g of a 95%borane--dimethyl sulfide mixture were heated on a steam bath for 11/2hours and then allowed to stand over the weekend. The reaction mixturewas poured into 100 ml of 5% HCl and heated on a steam bath. Thereaction mixture was made basic by the addition of anhydrous potassiumcarbonate, extracted with diethyl ether and dried. Analysis by thinlayer chromatography showed a trace of starting materials. The reductionreaction was repeated to give ##STR23##

A mixture of 0.8 g (0.0027 m) of this product, 0.57 g (0.0014 m) ofdichlorosulfonefluorescein, 0.05 g of magnesium oxide and 29 ml ofdimethylsulfoxide was heated at about 135° C. for about 31/2 hours. Anadditional 0.8 g of the previous product was added and heating continuedfor an additional 21/2 hours. The reaction mixture was removed from thesteam bath and stored in a nitrogen atmosphere for three days.

More of the previous product was added to the reaction mixture and itwas heated again on a steam bath. Sulfanilic acid (0.5 g) was added tothe reaction mixture and it was heated for about 1 hour. Thin layerchromatography showed that the orange monochloro-compond was gone. Thereaction mixture was added to a water-dilute HCl solution and the dyewas collected by filtration and dried. The dye was dissolved inchloroform and eluted from activated magnesium silicate (10/90methanol/chloroform, by volume). The solvent was evaporated from thepure dye fraction to give the pure dye having the formula ##STR24##

The dye (1.7 g, 0.00183 m) was dissolved in 65 ml chloroform, cooled to-55° C. on a dry ice/acetone bath and to the solution there were addedslowly 4.5 g (0.0183 m) of boron tribromide. The reaction mixture wasallowed to warm to room temperature and stirred for 4-5 hours. Water anddilute HCl were added to the reaction mixture and it was heated for 1/2hour on a steam bath. The dye developer (dye II) precipitated fromsolution, was collected by filtration, washed by stirring in 5% sodiumbicarbonate for 15-30 minutes, collected again by filtration, washedwith water and dried. The yield was quantitative. The dye developerexhibited λ_(max) =557 nm, ε=84,000 (methyl cellosolve).

A film unit was prepared wherein the negative element comprised asubcoated transparent photographic film base; a magenta dye developerlayer comprising about 265 mg./m² of dye developer II and about 265mg./m² of cellulose acetate hydrogen phthalate, a green sensitivegelatino silver iodobromide (0.61 micron) emulsion layer coated at acoverage of about 807 mg./m² of silver and about 956 mg./m² of gelatin;and an overcoat of about 323 mg./m² of gelatin and about 81 mg./m² of4'-methylphenylhydroquinone.

The image-receiving element was identical to that described in ExampleI.

The film unit was processed in the manner described in Example I usingthe same processing composition with the exception that the exposures ofthe negative element were to green and blue light successively. Therewas obtained a well defined magenta image (reflection density to greenlight D_(max) =1.81, D_(min) =0.40) which was visible through thetransparent base of the image-receiving element.

EXAMPLE III

6.0 gms (0.010 m) of ##STR25## were dissolved in tetrahydrofuran and 1equivalent (1.0 gm, 0.01028 m) of triethylamine added. To the solutionthere were added 2.5 gms (0.01028 m) of ##STR26## and the mixture wasleft stirring overnight. Ether (about 50 ml) was added and the solid wasfiltered off through diatomaceous earth. The solution was evaporatedunder vacuum to give an oily residue which is represented by the formula##STR27##

The oily residue was dissolved in about 100 ml of methanol. Hydrochloricacid gas was bubbled into the solution for about 10 minutes and thesolution was stirred overnight. The solvent was removed under vacuum andsubsequently the residue was stirred with diethyl ether and potassiumcarbonate. The ether layer was isolated and dried over anhydrous calciumsulfate. Thin layer chromatography (5/95 methanol/chloroform, by volume)showed one major spot and several minor spots. The material wascollected by filtration and the solvent evaporated off to give 5.0 gmsof a compound represented by the formula ##STR28##

A mixture of 5 gms of this product, 1.4 gms ofdichlorosulfonefluorescein, 0.14 gm of magnesium oxide and 10 mldimethylsulfoxide was allowed to stand overnight and then heated on asteam bath for three hours. To the reaction mixture there were added 3.0gms of indolene-5-sulfonic acid and heating was continued for anadditional 15 minutes. The reaction mixture was allowed to stand forabout two hours, then heated for 15 minutes, poured into water and thesolid collected by filtration and air dried. Chromatography on activatedmagnesium silicate (15/85 methanol/chloroform, by volume) gave 1.5 gmsof dye III, λ_(max) =630 nm, ε=76,000.

A film unit was prepared wherein the negative element comprised asubcoated transparent polyester photographic film base; a cyan dye layercoated at a coverage of about 850 mg./m² of dye III and about 850 mg./m²of cellulose acetate hydrogen phthalate; a gelatin layer coated at acoverage of about 646 mg./m² ; a blue sensitive gelatino silveriodobromide (1.66 microns) emulsion layer coated at a coverage of about215 mg./m² of silver and about 646 mg./m² of gelatin, and an overcoatlayer containing about 323 mg./m² of gelatin and about 27 mg./m² ofsuccinaldehyde.

The image-receiving element was the same as that described in Example I.

The film unit was processed with a processing composition comprising:

    ______________________________________                                                             GMS/100cc H.sub.2 O                                      ______________________________________                                        Water                  100 cc                                                 Sodium hydroxide       5.0                                                    Methylthiomethyl uracil                                                                              1.5                                                    Thiouracil             0.009                                                  Titanium dioxide       50.0                                                   Carboxymethyl hydroxyethyl cellulose                                                                 2.5                                                    Tetramethyl reductic acid                                                                            2.5                                                    Sodium sulfite         1.0                                                    ______________________________________                                    

The film unit was processed in the manner described in Example I withthe exception that the negative was exposed to the test target with bluelight only. After the 10 minute imbibition period the image appearedyellowish and then color shifted to cyan upon standing for 24 hoursunder ambient conditions. The resultant image was very well defined andhad a reflection density to red light D_(max) =2.72, D_(min) =0.33.

EXAMPLE IV

Under nitrogen atmosphere AlCl₃ (100 g, 0.75 m) was stirred in 200 ml ofcarbon disulfide while 45 ml (0.62 m) of acetyl chloride were addeddropwise. To the mixture there were added slowly 40 g (0.25 m) of##STR29## and the mixture mechanically stirred under gentle reflux untilthe mixture became a gum which could no longer be stirred (about 2hours). The mixture was then allowed to continue gentle refluxingovernight. After cooling the carbon disulfide was decanted and the flaskwas allowed to set in the open for several hours. An icewater mixturecontaining 66 ml of conc. HCl was then poured into the flask and theresulting hydrolyzed product was transferred to a beaker, stirred for ashort time, collected by filtration and washed with water. The solid wasrecrystallized from 2-propanol and dried to give 33 g (65% yield) of##STR30##

A solution of 18 g (0.089 m) of this product and 9.0 g (0.089 m) of##STR31## in about 200 ml of ethanol was formed. HCl gas was bubbledinto the solution until a solid began to form (about 5 min.). Thesolution was stirred for an additional 15 minutes, cooled and the solidproduct collected by filtration and washed with ethanol. The solid wasrecrystallized from boiling methyl cellosolve to give 7.8 g (35% yield)of ##STR32##

A mixture of 16 g (0.064 m) of this product in about 200 ml of aceticacid with 7 ml of acetic anhydride was reduced under a pressure of 40psi of hydrogen using 30% Pd/C as catalyst. The reduction was carriedout at room temperature until 2 equivalents of hydrogen were taken upfollowed by heating with steam. The resulting clear liquid mixture wasfiltered into water and stirred while neutralizing with potassiumhydroxide. The white solid which formed ##STR33## was collected byfiltration, washed with water and recrystallized from 2-propanol.

A mixture of 10 g (0.0295 m) of this product in 100 ml of a solution of25 ml water, 25 ml of conc. HCl and 50 ml of ethanol was refluxedovernight. The resulting solution was made alkaline with potassiumhydroxide solution, taken up in ether, dried and the solvent removed togive 7 g (80% yield) of a clear liquid ##STR34##

This product (7.0 g, 0.024 m) was dissolved in chloroform and thesolution cooled to -78° C. A solution of 7 ml of boron tribromide in 50ml of chloroform was added dropwise with stirring and the mixture wasallowed to reach room temperature and stirred overnight. To the mixturethere were added 100 ml of water containing about 10 ml of conc. HCl andthe mixture refluxed for 1 hour. The aqueous layer was separated,deaerated with N₂ and basicified with 5% NaHCO₃ solution. The resultingsolid ##STR35## was collected by filtration, washed well with degassedwater and allowed to air dry. The yield was 4.8 g (75%).

A mixture of 4.8 g (0.018 m) of this product, 3.4 g (0.008 m) ofdichlorosulfone fluorescein and 0.34 g of magnesium oxide was combinedwith 100 ml of degassed methanol and refluxed with stirring. Animmediate formation of a violet adduct occurred. The reaction wasfollowed by thin layer chromatography (10/90 methanol/chloroform, byvolume, as eluent). Conversion to the cyan desired product (Dye VII) wasincomplete after an 8-hour period. Degassed methyl cellosolve (100 ml)was added and the mixture heated while bubbling in nitrogen gas to driveoff methanol. When all the methanol was driven off the mixture wasallowed to continue refluxing until the initial violet adduct was gone.The mixture was allowed to cool, and filtered to collect the solid dyedeveloper which was washed with ether and dried to give 5.0 g (68%) ofDye VII λ_(max) =642 nm, ε=71,000.

Although the invention has been described with respect to specificpreferred embodiments, it is not intended to be limited thereto butrather those skilled in the art will recognize that variations andmodifications may be made therein which are within the spirit of theinvention and the scope of the appended claims.

What is claimed is:
 1. A diffusion transfer color process comprising:(a)imagewise exposing a photosensitive element including a silver halideemulsion and an image dye-providing material containing at least onediffusion control moiety and which is capable of providing a diffusibleimage dye containing the chromophoric system represented by the formula##STR36## wherein A is ##STR37## X is H, alkyl, phenyl, naphthyl,substituted phenyl or substituted naphthyl; W is H or alkyl; R is H oralkyl; and m and n are each integers of from 2 to 6, (b) developing saidexposed photosensitive element with an aqueous alkaline processingcomposition; (c) forming an imagewise distribution of said diffusibleimage dye from said image dye-providing material as a function of saiddevelopment; and (d) transferring at least a portion of said imagewisedistribution of said diffusible image dye to an image receiving layerarranged in superposed relationship with said silver halide emulsion toprovide a diffusion transfer dye image.
 2. The diffusion transfer colorprocess as defined in claim 1 wherein X is ##STR38## wherein R₁ is H,SO₃.sup.⊖, CO₂.sup.⊖ or alkyl.
 3. The diffusion transfer color processas defined in claim 2 wherein R₁ is SO₃.sup.⊖.
 4. The diffusion transfercolor process as defined in claim 1 wherein said image dye-providingmaterial is a compound represented by the formula ##STR39## wherein B is##STR40## each Y is a substituent containing a diffusion control moiety,each q is 0 or 1 provided that at least one q is 1, W is H or alkyl, Ris H or alkyl, R₁ is H, SO₃.sup.⊖, CO₂.sup.⊖ or alkyl and m and n areeach integers of from 2 to
 6. 5. The diffusion transfer color process asdefined in claim 4 wherein R₁ is SO₃.sup.⊖.
 6. The diffusion transfercolor process as defined in claim 4 wherein said image dye-providingmaterial is a dye developer, said diffusion control moiety being asilver halide developing moiety.
 7. The diffusion transfer color processas defined in claim 6 wherein said diffusion control substituent Y isthe group -E-Dev wherein Dev is a hydroquinonyl group and E is acovalent bond or a divalent linking group.
 8. The diffusion transfercolor process as defined in claim 6 wherein said dye developer isrepresented by the formula ##STR41##
 9. The diffusion transfer colorprocess as defined in claim 6 wherein said dye developer is representedby the formula ##STR42##
 10. The diffusion transfer color process asdefined in claim 6 wherein said dye developer is represented by theformula ##STR43##
 11. The diffusion transfer color process as defined inclaim 4 wherein said photosensitive element comprises a red-sensitivesilver halide emulsion associated with a cyan dye developer, agreen-sensitive silver halide emulsion associated with a magenta dyedeveloper, and a blue-sensitive silver halide emulsion associated with ayellow dye developer, and said diffusion transfer dye image is amulticolor image.
 12. The diffusion transfer color process as defined inclaim 4 wherein said diffusion control moiety is a color couplingmoiety.
 13. The diffusion transfer color process as defined in claim 12wherein said image dye-providing material is diffusible in said aqueousalkaline processing composition.
 14. The diffusion transfer colorprocess as defined in claim 12 wherein said image dye-providing materialis nondiffusible in said aqueous alkaline processing composition. 15.The diffusion transfer color process as defined in claim 4 wherein saidimage dye-providing material is nondiffusible and said diffusion controlmoiety is a sulfonamido phenol group.
 16. The diffusion transfer colorprocess as defined in claim 4 wherein said image dye-providing materialis nondiffusible and said diffusion control moiety is a thiazolidinegroup.
 17. The diffusion transfer color process as defined in claim 16wherein said image dye-providing material is represented by the formula##STR44##
 18. A photosensitive element comprising a support, a silverhalide emulsion in a layer carried by said support and an imagedye-providing material containing at least one diffusion control moietyin a layer carried by said support on the same side thereof as saidsilver halide emulsion, said image dye-providing material being capableof providing an image dye containing the chromophoric system representedby the formula ##STR45## wherein A is ##STR46## X is H, alkyl, phenyl,naphthyl, substituted phenyl or substituted naphthyl; W is H or alkyl; Ris H or alkyl; and m and n are each integers of from 2 to
 6. 19. Thephotosensitive element as defined in claim 18 wherein X is ##STR47##wherein R₁ is SO₃.sup.⊖, CO₂.sup.⊖ or alkyl.
 20. The photosensitiveelement as defined in claim 19 wherein R₁ is SO₃ ⁻.
 21. Thephotosensitive element as defined in claim 18 wherein said imagedye-providing material is a compound represented by the formula##STR48## wherein B is ##STR49## each Y is a substituent containing adiffusion control moiety, each q is 0 or 1 provided that at least one qis 1, W is H or alkyl, R is H or alkyl, R₁ is H, SO₃.sup.⊖, CO₂.sup.⊖ oralkyl and m and n are each integers of from 2 to
 6. 22. Thephotosensitive element as defined in claim 21 wherein R₁ is SO₃ ⁻. 23.The photosensitive element as defined in claim 21 wherein said imagedye-providing material is a dye developer, said diffusion control moietybeing a silver halide developing moiety.
 24. The photosensitive elementas defined in claim 23 wherein said diffusion control substituent Y isthe group -E-Dev wherein Dev is a hydroquinonyl group and E is acovalent bond or a divalent linking group.
 25. The photosensitiveelement as defined in claim 23 wherein said dye developer is representedby the formula ##STR50##
 26. The photosensitive element as defined inclaim 25 wherein said dye developer is represented by the formula##STR51##
 27. The photosensitive element as defined in claim 23 whereinsaid dye developer is represented by the formula ##STR52##
 28. Thephotosensitive element as defined in claim 21 including a red-sensitivesilver halide emulsion layer associated with a cyan dye developer layer,a greensensitive silver halide emulsion layer associated with a magentadye developer layer and a blue-sensitive silver halide emulsion layerassociated with a yellow dye developer layer.
 29. The photosensitiveelement as defined in claim 21 wherein said diffusion control moiety isa color coupling moiety.
 30. The photosensitive element as defined inclaim 21 wherein said diffusion control moiety is a sulfonamidophenolgroup.
 31. The photosensitive element as defined in claim 21 whereinsaid diffusion control moiety is a thiazolidine group.
 32. A diffusiontransfer color film unit comprising(a) a photosensitive element asdefined in claim 18; (b) a second sheet-like element adapted to besuperposed on said photosensitive element during or after photoexposure;(c) an image-receiving layer positioned in one of said photosensitive orsheet-like elements; and (d) a rupturable container releasably holdingan aqueous alkaline processing composition and so positioned as to beadapted to distribute said processing composition between predeterminedlayers of said elements.
 33. The film unit as defined in claim 32wherein said second sheet-like element comprises said image-receivinglayer carried on a transparent support, and said processing compositionincludes a light reflecting pigment adapted to provide a whitebackground against which an image formed in said image-receiving layermay be viewed through said transparent support.